CN112175186B - Polyimide material and preparation method thereof, polyimide film and preparation method thereof - Google Patents
Polyimide material and preparation method thereof, polyimide film and preparation method thereof Download PDFInfo
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- CN112175186B CN112175186B CN202011180380.3A CN202011180380A CN112175186B CN 112175186 B CN112175186 B CN 112175186B CN 202011180380 A CN202011180380 A CN 202011180380A CN 112175186 B CN112175186 B CN 112175186B
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- diamine compound
- polyimide
- polyimide film
- polyamic acid
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 134
- 239000004642 Polyimide Substances 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- -1 diamine compound Chemical class 0.000 claims abstract description 68
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 29
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims description 80
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 39
- 239000000843 powder Substances 0.000 claims description 28
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 26
- 125000002723 alicyclic group Chemical group 0.000 claims description 22
- 239000003822 epoxy resin Substances 0.000 claims description 21
- 229920000647 polyepoxide Polymers 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 230000018044 dehydration Effects 0.000 claims description 15
- 238000006297 dehydration reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 238000007363 ring formation reaction Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 5
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000010 aprotic solvent Substances 0.000 claims description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 claims description 2
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 claims description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 2
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 claims description 2
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000010345 tape casting Methods 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000203 mixture Substances 0.000 description 22
- 239000011521 glass Substances 0.000 description 18
- 238000001556 precipitation Methods 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 238000002834 transmittance Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 10
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 238000002791 soaking Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- GLXYOFXNKBTMQL-YKCHQESGSA-N (2S)-2-[[(2S)-2-[[(2S)-2-[[(2S)-1-[(2S)-6-amino-2-[[(2S)-4-amino-2-[[(2S)-2-[[(2S)-2-[[2-[[(2S)-1-[(2S)-6-amino-2-[[(2S,3S)-2-[[(2S)-2-[[(2S)-2-[[(2S)-2-amino-4-methylsulfanylbutanoyl]amino]-3-methylbutanoyl]amino]-5-(diaminomethylideneamino)pentanoyl]amino]-3-methylpentanoyl]amino]hexanoyl]pyrrolidine-2-carbonyl]amino]acetyl]amino]-3-hydroxypropanoyl]amino]propanoyl]amino]-4-oxobutanoyl]amino]hexanoyl]pyrrolidine-2-carbonyl]amino]-3-hydroxypropanoyl]amino]-3-carboxypropanoyl]amino]butanedioic acid Chemical compound CSCC[C@H](N)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CCCCN)C(=O)N1CCC[C@H]1C(=O)NCC(=O)N[C@@H](CO)C(=O)N[C@@H](C)C(=O)N[C@@H](CC(N)=O)C(=O)N[C@@H](CCCCN)C(=O)N1[C@H](C(=O)N[C@@H](CO)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CC(O)=O)C(O)=O)CCC1 GLXYOFXNKBTMQL-YKCHQESGSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Abstract
The invention provides a polyimide material and a preparation method thereof, and a polyimide film and a preparation method thereof. The polyimide material comprises raw materials of tetracarboxylic dianhydride, a first diamine compound and a second diamine compound; the structural formula of the first diamine compound is as follows:
Description
Technical Field
The invention relates to the field of new materials, in particular to a polyimide material and a preparation method thereof, and a polyimide film and a preparation method thereof.
Background
At present, the development of photoelectric devices gradually shows the trend of light weight, large scale, ultra-thin and flexibility, the glass used as the traditional transparent substrate material can not meet the development requirement of the future flexible packaging technology, and the high-transparency polymer material becomes the first choice of the future flexible photoelectric packaging substrate material due to the advantages of transparency, flexibility, light weight, high impact resistance and the like. However, the conventional high-transparency polymer materials such as polymethyl methacrylate, polystyrene, polycarbonate, etc. cannot meet the requirements of high-temperature processes such as electrode film deposition, annealing treatment, etc. in the processing process of photoelectric devices due to low heat-resistant temperature. Polyimide is a resin having excellent thermal dimensional stability because of its rigid chemical structure and containing a large number of aromatic ring structures, and has been widely used in fields requiring high dimensional stability (low linear expansion coefficient) such as a substrate film of a flexible printed circuit board and an interlayer insulating film of a semiconductor. However, the intense coloration due to intramolecular conjugation and intramolecular/intermolecular charge transfer interactions makes it difficult to apply the coloring to the optical field. Therefore, the development of transparent polyimide materials with low thermal expansion coefficient is the focus of research and development.
In view of this, the present application is specifically proposed.
Disclosure of Invention
The invention aims to provide a polyimide material and a preparation method thereof, and a polyimide film and a preparation method thereof, so as to solve the problems.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a polyimide material comprises raw materials of tetracarboxylic dianhydride, a first diamine compound and a second diamine compound; the structural formula of the first diamine compound is as follows:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R 8 Are all selected from H or CF 3 And R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R 8 At least one of them is CF 3 ；
The second diamine compound is free of ester bonds but contains CF 3 The diamine compound of (1).
Alternatively, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R 8 There may be 1, 2, 3,4, 5, 6, 7, 8CF 3 。
The preparation method of the first diamine compound includes: reacting the compound A with the compound B in the presence of a dehydrating agent (such as dicyclohexylcarbodiimide), a catalyst (such as 4-dimethylaminopyridine) and a solvent (such as dichloromethane) at 20-80 ℃ to obtain a compound C, and performing catalytic hydrogenation reaction on the compound C (the catalyst can be selected from Pd/C) to obtain the first diamine compound; wherein, the structural general formula of the compound A is as follows:
the structural general formula of the compound B is as follows:
the structural general formula of the compound C is as follows:
preferably, the tetracarboxylic dianhydride comprises an aromatic tetracarboxylic dianhydride and/or an alicyclic tetracarboxylic dianhydride;
preferably, the tetracarboxylic dianhydride comprises one or more of the compounds represented by structural formulae D-1 to D-17:
preferably, the second diamine compound comprises one or more of the compounds represented by structural formulae A-1 to A-13:
the second diamine compound with trifluoromethyl can raise the transparency of polyimide film.
Preferably, the first diamine compound comprises one or more of the compounds of formulae ii-1 to ii-13:
preferably, the ratio of the molar amount of the tetracarboxylic dianhydride to the total molar amount of the first diamine compound and the second diamine compound is (0.75 to 1.10): 1;
preferably, the ratio of the molar amount of the tetracarboxylic dianhydride to the total molar amount of the first diamine compound and the second diamine compound is (0.9 to 1.0): 1;
preferably, the molar amount of the first diamine compound accounts for 10% -90% of the total molar amount of the first diamine compound and the second diamine compound;
preferably, the molar amount of the first diamine compound is 30% -60% of the total molar amount of the first diamine compound and the second diamine compound.
Alternatively, the ratio of the molar amount of the tetracarboxylic dianhydride to the total molar amount of the first diamine compound and the second diamine compound may be 0.75: 1. 0.80: 1. 0.85: 1. 0.90: 1. 0.95: 1. 1.00: 1. 1.05: 1. 1.10:1 and (0.75-1.10): any value between 1; the proportion of the molar amount of the first diamine compound to the total molar amount of the first diamine compound and the second diamine compound may be any value between 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, and 10% to 90%.
A preparation method of the polyimide material comprises the following steps:
mixing raw materials including a first diamine compound, a second diamine compound and tetracarboxylic dianhydride, and reacting to obtain polyamic acid;
and (3) mixing the materials including the polyamic acid and the dehydrating agent, dehydrating and cyclizing to obtain the polyimide material.
Preferably, the preparation method of the polyamic acid comprises:
mixing raw materials including a first diamine compound, a second diamine compound and a first solvent to obtain a diamine monomer solution;
mixing materials including the diamine monomer solution and tetracarboxylic dianhydride, and reacting to obtain the polyamic acid;
preferably, the diamine monomer solution is prepared under protective atmosphere conditions;
preferably, the first solvent comprises an aprotic solvent and/or a phenolic solvent;
preferably, the aprotic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, tetramethylurea, hexamethylphosphoric triamide, gamma-butyrolactone, and the phenolic solvent comprises one or more of m-methylphenol, xylenol, phenol, halogenated phenols;
preferably, the first solvent is selected from one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide;
preferably, the polyamic acid has a solid content of 5wt% to 50wt%;
preferably, the polyamic acid has a solid content of 10wt% to 30wt%;
preferably, the reaction temperature is-20 ℃ to 100 ℃ and the reaction time is 4-48h;
preferably, the reaction temperature is 0-80 ℃ and the reaction time is 4-12h;
preferably, the temperature of the reaction is 20-60 ℃ and the time is 8-12h;
alternatively, the content of the solid in the polyamic acid may be any one of 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, and 5wt% to 50wt%; the reaction temperature can be any value between-20 ℃, 10 ℃,0 ℃, 10 ℃,20 ℃,30 ℃,40 ℃,50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ and-20 ℃ to 100 ℃, and the time can be any value between 4h, 8h, 12h, 16h, 20h, 24h, 28h, 30h, 36h, 40h, 44h, 48h and 4-48 h.
Preferably, the dehydrating agent comprises an acid anhydride;
preferably, the anhydride comprises one or more of acetic anhydride, propionic anhydride, trifluoroacetic anhydride;
preferably, the anhydride is acetic anhydride;
preferably, the molar amount of the dehydrating agent is 1 to 20 times that of the tetracarboxylic dianhydride;
alternatively, the molar amount of the dehydrating solvent may be any one of 1 time, 5 times, 10 times, 15 times, 20 times, and 1 to 20 times the molar amount of the tetracarboxylic dianhydride.
Preferably, the system for dehydration cyclization further comprises a dehydration ring-closing catalyst;
preferably, the dehydration ring closure catalyst comprises a tertiary amine;
preferably, the tertiary amine comprises one or more of pyridine, collidine, lutidine and triethylamine;
preferably, the tertiary amine is pyridine;
preferably, the molar amount of the dehydration ring-closure catalyst is 1 to 10 times that of the tetracarboxylic dianhydride;
alternatively, the molar amount of the dehydration ring-closing catalyst may be any one of 1 time, 5 times, 10 times, 15 times, 20 times, and 1 to 20 times the molar amount of the tetracarboxylic dianhydride.
Preferably, the reaction temperature of the dehydration cyclization is 0-180 ℃, and the time is 0.5-48h;
preferably, the reaction temperature of the dehydration and cyclization is 30-180 ℃ and the time is 4-48h;
preferably, the reaction temperature of the dehydration cyclization is 60-120 ℃, and the time is 4-12h;
preferably, the imidization rate of the polyimide material is greater than or equal to 50%;
preferably, the imidization rate of the polyimide material is 70% or more;
preferably, the imidization rate of the polyimide material is 88-95%;
alternatively, the reaction temperature of the dehydrocyclization may be any value between 0 ℃, 10 ℃,20 ℃,30 ℃,40 ℃,50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃,150 ℃, 160 ℃, 170 ℃, 180 ℃ and 0-180 ℃, and the time may be any value between 0.5, 1h, 2h, 4h, 8h, 12h, 16h, 20h, 24h, 28h, 32h, 36h, 40h, 44h, 48h and 0.5-48h; the imidization rate of the polyimide material may be any of 50%, 60%, 70%, 80%, 90%, 100%, and 50% or more.
Preferably, the polyimide material and a second solvent are mixed, and then the mixture is precipitated, filtered and dried to obtain polyimide powder;
preferably, the second solvent comprises ethanol.
A method for preparing a polyimide film, comprising:
and heating raw materials including the polyimide material to prepare the polyimide film.
Preferably, the solid content of the mixing system is 5wt% to 40wt%;
preferably, the solid content of the mixing system is 10wt% to 20wt%;
alternatively, the solids content of the mixing system may be any value between 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, and 5wt% to 40 wt%.
Preferably, the raw material further comprises a cycloaliphatic epoxy resin;
the alicyclic epoxy resin is added, and crosslinking curing is carried out in the heat treatment of film forming, so that the thermal expansion coefficient of the polyimide film is further reduced, and the solvent resistance, the mechanical property and the transparency are improved.
Preferably, the cycloaliphatic epoxy resin comprises one or more of the compounds of structural formulae E-1 to E-9:
preferably, the alicyclic epoxy resin comprises one or more compounds shown in structural formulas E-3, E-6 and E-7;
preferably, the amount of the alicyclic epoxy resin is 1-10% of the mass of the polyimide material;
preferably, the amount of the alicyclic epoxy resin is 5-8% of the mass of the polyimide material;
preferably, the heating adopts temperature programming: each gradient is set at 20-100 deg.C, the heating time of each gradient is 10-60min, and the end temperature is 50-500 deg.C;
preferably, there is one gradient per 50 ℃ and the heating time per gradient is 30min;
alternatively, the alicyclic epoxy resin may be used in an amount of 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, and any value between 1% and 10% by mass of the polyimide material; in the programmed heating, each gradient may be set to any one of 20 ℃,30 ℃,40 ℃,50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ and 20-100 ℃, the heating time of each gradient may be set to any one of 10min, 20min, 30min,40 min,50 min, 60min and 10-60min, and the end point temperature may be set to any one of 50 ℃, 100 ℃,150 ℃,200 ℃,250 ℃,300 ℃,350 ℃,400 ℃,450 ℃,500 ℃ and 50-500 ℃.
Preferably, the feedstock further comprises a third solvent comprising one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, tetramethylurea, hexamethylphosphoric triamide, gamma-butyrolactone;
preferably, the third solvent comprises one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide;
preferably, the polyimide film is prepared by a casting method in a protective atmosphere.
A polyimide film is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
according to the polyimide material provided by the application, tetracarboxylic dianhydride, a first diamine compound and a second diamine compound are used as monomers, and an aromatic ester bond and a trifluoromethyl group are introduced in the molecular structure design, so that the thermal expansion coefficient of the polyimide material after being prepared into a film is reduced, the solvent resistance and the mechanical property of the polyimide material are improved, and the original transparent property of the polyimide material can be maintained.
The preparation method of the polyimide material is simple to operate;
according to the polyimide film and the preparation method thereof, the polyimide film with low thermal expansion coefficient, good solvent resistance and mechanical properties and high transparency is obtained by using the polyimide material with aromatic ester bonds and trifluoromethyl groups.
Detailed Description
The terms as used herein:
"consisting of 8230%" \8230, preparation "and" comprising "are synonymous. As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of 823070, 8230composition" excludes any unspecified elements, steps or components. If used in a claim, this phrase shall render the claim closed except for the materials described except for those materials normally associated therewith. When the phrase "consisting of 8230' \8230"; composition "appears in a clause of the subject matter of the claims and not immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4," "1 to 3," "1 to 2 and 4 to 5," "1 to 3 and 5," and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent an arbitrary unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is not to be misunderstood that the sum of the parts by mass of all the components is not limited to the limit of 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
The structures and abbreviations of the main compounds used in the following examples:
dianhydride compound:
6FDA:4,4' - (hexafluoroisopropylidene) diphthalic anhydride, having the formula:
diamine compound (b):
TFMB:2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, having the structural formula:
APAB:4,4' -diaminobenzoic acid phenyl ester, the structural formula is:
APAB-CF 3 :3 '-trifluoromethyl-4, 4' -diaminobenzoic acid phenyl ester, the structural formula is:
APAB-2CF 3 : phenyl 3,3 '-bis (trifluoromethyl) -4,4' -diaminobenzoate, having the structural formula:
APAB-8CF 3 : phenyl 2,2', 3', 5', 6' -octa (trifluoromethyl) -4,4' -diaminobenzoate having the formula:
alicyclic epoxy resin:
TTA60:1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexanecarboxylic acid) ester having the structural formula:
solvent:
NMP: n-methyl-2-pyrrolidone.
Example 1
TFMB (14.4 g, 0.045mol) and APAB-CF were added to a three-necked flask under a nitrogen atmosphere at room temperature 3 (1.48g, 0.005mol) and NMP (152.38 g) were stirred at room temperature for 30min to confirm complete dissolution, and 6FDA (22.2g, 0.05mol) was added thereto, and the reaction was stirred at room temperature for 4 hours to obtain a transparent viscous polyamic acid solution having a solid content of 20 wt%.
NMP (22.11 g) was further added to the above polyamic acid solution, and stirred at room temperature for 30min to confirm uniform mixing, followed by addition of acetic anhydride (14.8 g) and pyridine (25.5 g) for chemical imidization, and reaction at room temperature for 2 hours. And after the reaction is finished, pouring the reaction solution into ethanol for precipitation, filtering the solution after precipitation, collecting the solid, soaking and washing the solid twice by using ethanol, filtering, and drying under reduced pressure in a vacuum oven at 60 ℃ for 12 hours to obtain polyimide solid powder PI-1 (imidization rate is 93.6%).
Taking the dried polyimide solid powder PI-1 and alicyclic epoxy resin TTA60 with the polyimide mass of 6%, preparing a solution with the solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the nitrogen protection atmosphere to obtain the transparent polyimide film PIF-1.
Example 2
TFMB (8g, 0.025mol) and APAB-CF were charged into a three-necked flask under a nitrogen atmosphere at room temperature 3 (7.4g, 0.025 mol) and NMP (150.4 g) were stirred at room temperature for 30min to confirm complete dissolution. Then 6FDA (22.2g, 0.05mol) is added, and the mixture is stirred and reacted for 4 hours at room temperature to obtain transparent viscous polyamic acid solution with the solid mass percentage of 20 weight percent.
NMP (21.37 g) was further added to the above polyamic acid solution, and the mixture was stirred at room temperature for 30min to confirm uniform mixing, followed by addition of acetic anhydride (15.1 g) and pyridine (25.5 g) to conduct chemical imidization, and then the reaction was carried out at room temperature for 2 hours. And after the reaction is finished, pouring the reaction solution into a large amount of ethanol for precipitation, filtering the solution after precipitation, collecting the solid, soaking and washing the solid twice by using a large amount of ethanol, filtering, and drying under reduced pressure for 12 hours in a vacuum oven at 60 ℃ to obtain polyimide solid powder PI-2 (the imidization rate is 95.3%).
Taking the dried polyimide solid powder PI-2 and alicyclic epoxy resin TTA60 with the polyimide mass of 6%, preparing a solution with the solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the nitrogen protection atmosphere to obtain the transparent polyimide film PIF-2.
Example 3
TFMB (1.6 g, 0.005mol), APAB-CF were added to a three-necked flask in a nitrogen atmosphere at room temperature 3 (13.32g, 0.045mol) and NMP (148.48 g) were stirred at room temperature for 30min to confirm complete dissolution. Then 6FDA (22.2g, 0.05mol) is added, and the mixture is stirred and reacted for 4 hours at room temperature to obtain transparent viscous polyamic acid solution with the solid mass percentage of 20 weight percent.
NMP (20.57 g) was further added to the above polyamic acid solution, and the mixture was stirred at room temperature for 30min to confirm uniform mixing, followed by addition of acetic anhydride (14.3 g) and pyridine (25.5 g) to conduct chemical imidization, and then the reaction was carried out at room temperature for 2 hours. And after the reaction is finished, pouring the reaction solution into a large amount of ethanol for precipitation, filtering the solution after precipitation, collecting the solid, soaking and washing the solid twice by using a large amount of ethanol, filtering, and drying under reduced pressure in a vacuum oven at 60 ℃ for 12 hours to obtain polyimide solid powder PI-3 (the imidization rate is 90.6%).
Taking the dried polyimide solid powder PI-3 and alicyclic epoxy resin TTA60 with the polyimide mass of 6%, preparing a solution with the solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the nitrogen protection atmosphere to obtain the transparent polyimide film PIF-3.
Example 4
TFMB (8g, 0.025mol) and APAB-2CF were charged into a three-necked flask under a nitrogen atmosphere at room temperature 3 (9.1g, 0.025 mol) and NMP (157.2 g), and stirred at room temperature for 30min to confirm complete dissolution. Then 6FDA (22.2g, 0.05mol) is added, and the mixture is stirred and reacted for 4 hours at room temperature to obtain transparent and viscous polyamide acid solution with the solid content of 20 weight percent.
NMP (24.2 g) was further added to the above polyamic acid solution, and the mixture was stirred at room temperature for 30min to confirm uniform mixing, followed by addition of acetic anhydride (14.5 g) and pyridine (25.5 g) to conduct chemical imidization, and then the reaction was carried out at room temperature for 2 hours. And after the reaction is finished, pouring the reaction solution into a large amount of ethanol for precipitation, filtering the solution after precipitation, collecting the solid, soaking and washing the solid twice by using a large amount of ethanol, filtering, and drying under reduced pressure for 12 hours at 60 ℃ in a vacuum oven to obtain polyimide solid powder PI-4 (imidization rate is 91.7%).
Taking the dried polyimide solid powder PI-4 and alicyclic epoxy resin TTA60 with the polyimide mass of 6%, preparing a solution with the solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the nitrogen protection atmosphere to obtain the transparent polyimide film PIF-4.
Example 5
TFMB (8g, 0.025mol) and APAB-8CF were charged into a three-necked flask under a nitrogen atmosphere at room temperature 3 (19.3 g, 0.025mol) and NMP (198 g) were stirred at room temperature for 30min to confirm complete dissolution. Then 6FDA (22.2g, 0.05mol) is added, and the mixture is stirred and reacted for 4 hours at room temperature to obtain transparent viscous polyamic acid solution with the solid mass percentage of 20 weight percent.
NMP (41.2 g) was further added to the above polyamic acid solution, and the mixture was stirred at room temperature for 30min to confirm uniform mixing, followed by addition of acetic anhydride (15.3 g) and pyridine (25.5 g) to conduct chemical imidization, and then the reaction was carried out at room temperature for 2 hours. And after the reaction is finished, pouring the reaction solution into a large amount of ethanol for precipitation, filtering the solution after precipitation, collecting the solid, soaking and washing the solid twice by using a large amount of ethanol, filtering, and drying under reduced pressure in a vacuum oven at 60 ℃ for 12 hours to obtain polyimide solid powder PI-5 (imidization rate is 96.7%).
Taking the dried polyimide solid powder PI-5 and alicyclic epoxy resin TTA60 with polyimide mass of 6%, preparing a solution with solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the protection of nitrogen to obtain the transparent polyimide film PIF-5.
Example 6
Taking the dried polyimide solid powder PI-1 obtained in the example 1, preparing a solution with the solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the protection of nitrogen to obtain the transparent polyimide film PIF-6.
Example 7
Taking the dried polyimide solid powder PI-2 obtained in the example 2, preparing a solution with the solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming on the solution at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the protection of nitrogen to obtain the transparent polyimide film PIF-7.
Example 8
Taking the dried polyimide solid powder PI-3 obtained in the embodiment 3, preparing a solution with the solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming on the solution at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the protection of nitrogen to obtain the transparent polyimide film PIF-8.
Example 9
Taking the dried polyimide solid powder PI-4 obtained in the embodiment 4, preparing a solution with the solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming on the solution at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the protection of nitrogen to obtain the transparent polyimide film PIF-9.
Example 10
Taking the dried polyimide solid powder PI-5 obtained in the example 5, preparing a solution with the solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming on the solution at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the protection of nitrogen to obtain the transparent polyimide film PIF-10.
Comparative example 1
TFMB (1693 g, 0.05mol) and NMP (152.8 g) were added to a three-necked flask under nitrogen atmosphere at room temperature, and the mixture was stirred at room temperature for 30min to confirm complete dissolution. Then 6FDA (22.2g, 0.05mol) is added, and the mixture is stirred and reacted for 4 hours at room temperature to obtain transparent viscous polyamic acid solution with the solid mass percentage of 20 weight percent.
NMP (22.37 g) was further added to the above polyamic acid solution, and the mixture was stirred at room temperature for 30min to confirm uniform mixing, followed by addition of acetic anhydride (14.5 g) and pyridine (25.5 g) to conduct chemical imidization, and then the reaction was carried out at room temperature for 2 hours. And after the reaction is finished, pouring the reaction solution into a large amount of ethanol for precipitation, filtering the solution after precipitation, collecting the solid, soaking and washing the solid twice by using a large amount of ethanol, filtering, and drying under reduced pressure in a vacuum oven at 60 ℃ for 12 hours to obtain polyimide solid powder PI-6 (imidization rate 91.8%).
Taking the dried polyimide solid powder PI-6 and alicyclic epoxy resin TTA60 with the polyimide mass of 6%, preparing a solution with the solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the nitrogen protection atmosphere to obtain the transparent polyimide film PIF-11.
Comparative example 2
APAB (32g, 0.05mol) and NMP (134.4 g) were added to a three-necked flask under nitrogen atmosphere at room temperature, and the mixture was stirred at room temperature for 30min to confirm complete dissolution. Then 6FDA (22.2g, 0.05mol) is added, and the mixture is stirred and reacted for 4 hours at room temperature to obtain transparent viscous polyamic acid solution with the solid mass percentage of 20 weight percent.
NMP (14.7 g) was further added to the above polyamic acid solution, and the mixture was stirred at room temperature for 30min to confirm uniform mixing, followed by addition of acetic anhydride (14.8 g) and pyridine (25.5 g) to conduct chemical imidization, and then the reaction was carried out at room temperature for 2 hours. And after the reaction is finished, pouring the reaction solution into a large amount of ethanol for precipitation, filtering the solution after precipitation, collecting the solid, soaking and washing the solid twice by using a large amount of ethanol, filtering, and drying under reduced pressure for 12 hours at 60 ℃ in a vacuum oven to obtain polyimide solid powder PI-7 (imidization rate is 93.6%).
Taking the dried polyimide solid powder PI-7 and alicyclic epoxy resin TTA60 with the polyimide mass of 6%, preparing a solution with the solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the nitrogen protection atmosphere to obtain the transparent polyimide film PIF-12.
Comparative example 3
Adding APAB-CF into a three-neck flask in a room temperature environment under a nitrogen atmosphere 3 (38.6 g, 0.05mol) and NMP (243.2 g) were stirred at room temperature for 30min to confirm complete dissolution. Then 6FDA (22.2g, 0.05mol) is added, and the mixture is stirred and reacted for 4 hours at room temperature to obtain transparent viscous polyamic acid solution with the solid mass percentage of 20 weight percent.
NMP (60.0 g) was further added to the above polyamic acid solution, and the mixture was stirred at room temperature for 30min to confirm uniform mixing, followed by addition of acetic anhydride (15.1 g) and pyridine (25.5 g) for chemical imidization and reaction at room temperature for 2 hours. And after the reaction is finished, pouring the reaction solution into a large amount of ethanol for precipitation, filtering the solution after precipitation, collecting a solid, soaking and washing the solid twice by using a large amount of ethanol, filtering, and drying under reduced pressure in a vacuum oven at 60 ℃ for 12 hours to obtain polyimide solid powder PI-8 (imidization rate is 95.1%).
Taking the dried polyimide solid powder PI-8 and alicyclic epoxy resin TTA60 with the polyimide mass of 6%, preparing a solution with the solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the nitrogen protection atmosphere to obtain the transparent polyimide film PIF-13.
Comparative example 4
TFMB (8g, 0.025 mol), APAB (5.7g, 0.025 mol) and NMP (143.6 g) were charged into a three-necked flask under a nitrogen atmosphere at room temperature, and stirred at room temperature for 30min to confirm complete dissolution. Then 6FDA (22.2g, 0.05mol) is added, and the mixture is stirred and reacted for 4 hours at room temperature to obtain transparent viscous polyamic acid solution with the solid mass percentage of 20 weight percent.
NMP (18.53 g) was further added to the above polyamic acid solution, and the mixture was stirred at room temperature for 30min to confirm uniform mixing, followed by addition of acetic anhydride (14.7 g) and pyridine (25.5 g) to conduct chemical imidization, and then the reaction was carried out at room temperature for 2 hours. And after the reaction is finished, pouring the reaction solution into a large amount of ethanol for precipitation, filtering the solution after precipitation, collecting the solid, soaking and washing the solid twice by using a large amount of ethanol, filtering, and drying under reduced pressure in a vacuum oven at 60 ℃ for 12 hours to obtain polyimide solid powder PI-9 (the imidization rate is 92.9%).
Taking the dried polyimide solid powder PI-9 and alicyclic epoxy resin TTA60 with polyimide mass of 6%, preparing a solution with solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the protection of nitrogen gas to obtain the transparent polyimide film PIF-14.
Comparative example 5
Taking the dried polyimide solid powder PI-6 obtained in the comparative example 1, preparing a solution with the solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the protection of nitrogen to obtain the transparent polyimide film PIF-15.
Comparative example 6
Taking the polyimide solid powder PI-7 dried in the comparative example 2, preparing a solution with the solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming on the solution at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the protection of nitrogen to obtain the transparent polyimide film PIF-16.
Comparative example 7
Taking the polyimide solid powder PI-8 dried in the comparative example 3, preparing a solution with the solid content of 20wt% by using NMP, uniformly coating the solution on a clean glass plate, and carrying out temperature programming on the solution at 100 ℃/30min,150 ℃/30min,200 ℃/30min,250 ℃/30min,300 ℃/30min,350 ℃/30min,400 ℃/30min,450 ℃/30min and 500 ℃/30min under the protection of nitrogen to obtain the transparent polyimide film PIF-17.
The polyimides and polyimide films obtained in examples and comparative examples were evaluated by the following methods:
(1) The polyimide imidization rate measuring method comprises the following steps:
the polyimide was dried at room temperature, dissolved in DMSO-d6, and 1H-NMR was measured at room temperature using tetramethylsilane as a reference substance, and the value was determined by the following formula (i):
imidization rate (%) = (1-A1/A2. Times. Alpha.) X100 (i)
A1: peak area of proton derived from NH group (10 ppm)
A2: peak area derived from other protons
α: the ratio of the number of other protons to 1 proton of the NH group in the precursor of the polymer (polyamic acid) was determined.
(2) Transmittance evaluation method:
a film having a thickness of 15 to 25 μm was cut into a sample of 40 mm. Times.40 mm, and the transmittance of the film was measured as the transmittance in the wavelength range of 200 to 800nm using an ultraviolet spectrophotometer (Carry, 300) and the transmittance in the range of 380 to 780 nm.
(3) Method for evaluating glass transition temperature Tg:
the glass transition temperature (Tg) of the film material was measured using a differential scanning calorimeter (NETZSCH, DSC 204F 1): the measuring temperature range is 150-450 ℃, and the heating rate is 10 ℃/min.
(4) Coefficient of thermal expansion CTE evaluation method:
measuring Coefficient of Thermal Expansion (CTE) by adopting a thermo-mechanical analyzer (TA, Q400), cutting a film with the thickness of 15-25 mu m into strip samples with the width of 10mm multiplied by 5mm, testing the temperature interval of 50-500 ℃, heating up speed of 10 ℃/min and 0.05N constant force stretching.
(5) Mechanical property evaluation method:
the mechanical properties of the films were tested using an electronic universal material tester (Instron 5567): tensile rate 5mm/min, load 100N, gauge length 20mm, and approximately 20 μm thick film was cut into 60mm by 10mm wide strip samples.
(6) Method for evaluating solvent resistance of polyimide film:
a film having a thickness of about 20 μm was cut into a square sample having a size of 20mm × 20mm, immersed in an organic solvent 10 times the weight of the film, immersed at room temperature for 30min, and examined as to whether the film was dissolved in the organic solvent or not, and was damaged.
The evaluation results are shown in tables 1 to 3 below:
TABLE 1 film transmittance, tg, CTE test results
From Table 1 above, byComparison of the transmittance data of example 4 with that of comparative example 1 shows that APAB-2CF, the first diamine compound, is absent from the monomers 3 In this case, the transmittance of the obtained polyimide film was decreased, indicating that the combined use of the first diamine compound and the second diamine compound can increase the transmittance of the polyimide film. As can be seen from the comparison of the transmittance data of comparative examples 2 and 3 and the comparison of the transmittance data of examples 1 to 3 and examples 4 to 5, the larger the amount of trifluoromethyl group in the diamine compound, the higher the transmittance of the polyimide film obtained. As can be seen from comparison of the transmittance data of examples 1 to 3 with comparative example 3, the transmittance of the polyimide film obtained using the first diamine compound and the second diamine compound in combination was higher than that of the polyimide film obtained using the first diamine compound alone, indicating that there was a synergistic effect between the two. As can be seen from the comparison of examples 1-5 with examples 6-10 and the comparison of comparative examples 1-3 with comparative examples 5-7, the addition of the cycloaliphatic epoxy resin TTA60 can significantly raise the Tg and lower the CTE of the film without changing the transparency of the film.
TABLE 2 film mechanical Property test results
From Table 2 above, it can be seen by comparing the mechanical property test data of example 4 with that of comparative example 1 that APAB-2CF is the first diamine compound when no monomer is contained 3 In the meantime, the mechanical property test of the obtained polyimide film is lowered, which indicates that the mechanical property of the polyimide film can be improved by using the first diamine compound and the second diamine compound in combination. As can be seen from the comparison of the mechanical property data of comparative examples 2 and 3 and the comparison of the mechanical property data of examples 1 to 3 and examples 4 to 5, the amount of trifluoromethyl group in the diamine compound does not necessarily correlate with the mechanical properties of the polyimide film. From the comparison of the mechanical property data of examples 1-3 with comparative example 3, it can be seen that the first diamine compound and the second diamine compound are combinedThe combination of the compounds has better mechanical property than the polyimide film prepared by singly using the first diamine compound, which indicates that the two compounds have synergistic effect. As can be seen from the comparison of examples 1 to 5 with examples 6 to 10 and the comparison of comparative examples 1 to 3 with comparative examples 5 to 7, the addition of TTA60, which is an alicyclic epoxy resin, can improve the mechanical properties of the polyimide film.
TABLE 3 film solvent resistance test results
From table 3 above, it can be seen that the addition of the cycloaliphatic epoxy resin TTA60 can significantly improve the solvent resistance of the film by comparing examples 1-5 with examples 6-10 and comparing comparative examples 1-3 with comparative examples 5-7.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (5)
1. A method for preparing a polyimide film is characterized by comprising the following steps:
heating raw materials including a polyimide material, and preparing the polyimide film in a protective atmosphere by adopting a tape casting method;
the preparation method of the polyimide material comprises the following steps:
mixing raw materials including a first diamine compound, a second diamine compound and tetracarboxylic dianhydride, and reacting to obtain polyamic acid;
mixing the materials including the polyamic acid and the dehydrating agent, dehydrating and cyclizing to obtain the polyimide material; mixing the polyimide material with a second solvent, and precipitating, filtering and drying to obtain polyimide powder; the second solvent comprises ethanol;
the preparation method of the polyamic acid comprises the following steps:
mixing raw materials including a first diamine compound, a second diamine compound and a first solvent under a protective atmosphere condition to prepare a diamine monomer solution; the first solvent comprises an aprotic solvent and/or a phenolic solvent;
mixing materials including the diamine monomer solution and tetracarboxylic dianhydride, and reacting to obtain the polyamic acid; in the polyamic acid, the solid content is 5-50 wt%; the reaction temperature is-20 ℃ to 100 ℃ and the reaction time is 4-48h;
the dehydrating agent comprises anhydride, and the molar weight of the dehydrating agent is 1-20 times of that of the tetracarboxylic dianhydride; the system for dehydration cyclization further comprises a dehydration ring-closing catalyst, and the dehydration ring-closing catalyst comprises tertiary amine; the molar weight of the dehydration ring-closing catalyst is 1 to 10 times of that of the tetracarboxylic dianhydride; the reaction temperature of the dehydration cyclization is 0-180 ℃, and the reaction time is 0.5-48h;
the imidization rate of the polyimide material is more than or equal to 50 percent;
the tetracarboxylic dianhydride comprises one or more of the compounds shown in structural formulas D-1 to D-17:
the second diamine compound comprises one or more of the compounds represented by structural formulae a-1 to a-13:
the first diamine compound comprises one or more of the compounds shown in structural formulas II-1 to II-13:
the ratio of the molar amount of the tetracarboxylic dianhydride to the total molar amount of the first diamine compound and the second diamine compound is (0.75 to 1.10): 1; the molar weight of the first diamine compound accounts for 10% -90% of the total molar weight of the first diamine compound and the second diamine compound;
the polyimide film is prepared from raw materials with the solid content of 5wt% -40wt%, and the polyimide film further comprises alicyclic epoxy resin, wherein the alicyclic epoxy resin comprises one or more compounds shown in structural formulas E-1 to E-9:
the amount of the alicyclic epoxy resin is 1-10% of the polyimide material by mass; when the polyimide film is prepared, the heating adopts temperature programming: each gradient is formed at the temperature of 20-100 ℃, the heating time of each gradient is 10-60min, and the end point temperature is 50-500 ℃; the raw materials for preparing the polyimide film also comprise a third solvent, wherein the third solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, tetramethylurea, hexamethylphosphoric triamide and gamma-butyrolactone.
2. The method of preparing a polyimide film according to claim 1, wherein the aprotic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, tetramethylurea, hexamethylphosphoric triamide, and γ -butyrolactone, and the phenolic solvent comprises one or more of m-methylphenol, xylenol, phenol, and halogenated phenol;
in the polyamic acid, the solid content is 10-30 wt%; the reaction temperature for obtaining the polyamic acid is 0-80 ℃, and the reaction time is 4-12h; the acid anhydride comprises one or more of acetic anhydride, propionic anhydride and trifluoroacetic anhydride; the tertiary amine comprises one or more of pyridine, collidine, lutidine and triethylamine; the reaction temperature of the dehydration and cyclization is 30-180 ℃, and the time is 4-48h; the imidization rate of the polyimide material is more than or equal to 70 percent; the ratio of the molar amount of the tetracarboxylic dianhydride to the total molar amount of the first diamine compound and the second diamine compound is (0.9-1.0): 1; the molar amount of the first diamine compound accounts for 30-60% of the total molar amount of the first diamine compound and the second diamine compound.
3. The method for producing a polyimide film according to claim 2, wherein the first solvent is one or more selected from the group consisting of N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide; the reaction temperature for obtaining the polyamic acid is 20-60 ℃, and the reaction time is 8-12h; the acid anhydride is acetic anhydride, and the tertiary amine is pyridine; the reaction temperature of the dehydration cyclization is 60-120 ℃, and the reaction time is 4-12h; the imidization rate of the polyimide material is 88-95%.
4. The production method according to claim 1, wherein the raw material from which the polyimide film is produced has a solid content of 10wt% to 20wt%;
the alicyclic epoxy resin comprises one or more compounds shown as structural formulas E-3, E-6 and E-7;
the amount of the alicyclic epoxy resin is 5-8% of the polyimide material by mass;
every 50 ℃ is a gradient, and the heating time of each gradient is 30min;
the third solvent comprises one or more of N-methyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
5. A polyimide film obtained by the production method according to any one of claims 1 to 4.
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